Activation of Methane by Os : Guided-Ion-Beam and Theoretical Studies.

Activation of methane by the third-row transition-metal cation Os is studied experimentally by examining the kinetic energy dependence of reactions of Os with CH and CD using guided-ion-beam tandem mass spectrometry. A flow tube ion source produces Os in its electronic ground state and primarily in the ground spin-orbit level. Dehydrogenation to form [Os,C,2 H] +H is exothermic, efficient, and the only process observed at low energies for reaction of Os with methane, whereas OsH dominates the product spectrum at higher energies.

Infrared multiple photon dissociation spectroscopy of cationized histidine: effects of metal cation size on gas-phase conformation.

The gas phase structures of cationized histidine (His), including complexes with Li(+), Na(+), K(+), Rb(+), and Cs(+), are examined by infrared multiple photon dissociation (IRMPD) action spectroscopy utilizing light generated by a free electron laser, in conjunction with quantum chemical calculations. To identify the structures present in the experimental studies, measured IRMPD spectra are compared to spectra calculated at B3LYP/6-311+G(d,p) (Li(+), Na(+), and K(+) complexes) and B3LYP/HW*/6-311+G(d,p) (Rb(+) and Cs(+) complexes) levels of theory, where HW* indicates that the Hay-Wadt effective core potential with additional polarization functions was used on the metals. Single point energy calculations were carried out at the B3LYP, B3P86, and MP2(full) levels using the 6-311+G(2d,2p) basis set.

Guided ion beam and theoretical study of the reactions of Os+ with H2, D2, and HD.

Reactions of the third-row transition metal cation Os(+) with H(2), D(2), and HD to form OsH(+) (OsD(+)) were studied using a guided ion beam tandem mass spectrometer. A flow tube ion source produces Os(+) in its (6)D (6s(1)5d(6)) electronic ground state level. Corresponding state-specific reaction cross sections are obtained.

Guided ion beam and theoretical study of the reactions of Au+ with H2, D2, and HD.

Reactions of the late third-row transition metal cation Au(+) with H(2), D(2), and HD are examined using guided ion beam tandem mass spectrometry. A flow tube ion source produces Au(+) in its (1)S (5d(10)) electronic ground state level. Corresponding state-specific reaction cross sections for forming AuH(+) and AuD(+) as a function of kinetic energy are obtained and analyzed to give a 0 K bond dissociation energy of D(0)(Au(+)-H) = 2.

Guided ion beam and theoretical study of the reactions of Hf+ with H2, D2, and HD.

The kinetic energy dependences of reactions of the third-row transition metal cation Hf(+) with H(2), D(2), and HD were determined using a guided ion beam tandem mass spectrometer. A flow tube ion source produces Hf(+) in its (2)D (6s(2)5d(1)) electronic ground state level. Corresponding state-specific reaction cross sections are obtained.